Indigoid dyestuff and process of preparing the same



Patented Oct. 1, 1929 uNrrEp STATES PATENT OFFICE ERWIN HOFFA, HANS HEYNA, AND FRITZ MULLER, OF HOCHST-ON-THE-MAIN, GER- MANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC.,

oonromrron or DELAWARE NEW YORK, N. Y., A

INDIGOID DYESTUFF PROCESS OF PREPARING BHE SAME No Drawing. Application filed November 30; 1326, Serial No. 151,824, and in Germany December 4, 1925.

Our present invention relates to new indigoid dyestuffs and a process of preparing the same. More particularly it relates to the indigoid dyestuffs of the general formula:

Hlg S 11 0 :O -Aih Hlg with a cyclic ortho-diketone, as for instance with an insatin or a 2.3-diketodihydrothionaphthene or a substitution product or a reactive (it-derivative thereof. The products thus obtainable may, if necessary, be further halogenated.

The following examples serve to illustrate our invention, but they are not intended to limit it thereto, all parts being by Weight:

1. A suspension of 15 parts of 4.5.6.7-tetrachlor-3-hydroxy-l-thionaphthene in. 30 parts of benzene is added to a solution of 5.7-dichlorisatin-a-chloride prepared from 11 parts of 5.7-dichlorisatin, 50 parts of benzene and 11 parts of phosphorus pentachloride. After having'heated the mixture for a short time the condensation is finished. The product is filtered and washed with benzene. The dyeis separated from the glacial acetic acid.

stuff thus obtainable corresponds most probably to the following formula:

It forms a violet powder and dissolves in concentrated siilfuric acid to a blue solution. It dyes cotton a violet tint of excellent properties as to fastness.

2. 14,4 parts of 4.5.6.7-tetrachlor-3-hydroXy-l-thionaphthene are heated to boiling in 150 parts of glacial acetic acid with 11 parts of 5.7-dichlorisatin and 2 parts of concentrated hydrochloric acid. As soon as the formation of the dyestufi is complete, the mass is cooled to 30t0 C. and the dyestufi' It forms a brown powder which is soluble in hot concentrated surfuric acid to a brown solution and-dyes cotton fast brown tints. Most probably it corresponds to the following formula:

S l c1 1 CAN chlor-3-hydroxy-l-thionaphthene until the formation of the dyestuff has ceased. The product is then cooled and the dyestuff separated from the glacial acetic acid. It

forms a violet powder dissolving inlhot concentrated sulfuric acid to a green solution and giving a vat from which cotton is dyed a violet tint.

Most probably it corresponds to the following formula:

In the following claims the term Fcyclic ortho-diketone is intended to comprise also i the substitution products and the reactive wderivati'ves of the cyclic orthodiketones. y

We claim: 7

1. Process of preparing indigoid dyestuffs which comprises condensing a 4.5.6.7-tetrahalogen-3-hydroxy-1-thionaphthene with a cyclic ortho-diketone.

2. Process of preparing indigoid dyest-uifs which comprises condensing a-4.5.6.7-tetra halogen-3hydroxy-l-thionaphthene isatin.

3. Process of preparing indigoid dyestuffs which comprisesfcondensing a l.5.6.7-tetrahalogen-3-hydroxy-l-thionaphthene with an isatin-a-derivative.

4. Process of preparing indigoid dyestuffs which comprises condensing a 4.5.6.7-tetrahalogen-3-hydr0xy-1-thionaphthene with a 5.7 -dihalogenisatin.

5. Process of preparing indigoid dyestuffs which comprises condensing a 4.5.6.7-tetrahalogen-3-hydroxy-1-thionaphthene with a ,5.7-dihalogenisatin-a-derivative.

6. Process of preparing indigoid dyestufi's which comprises condensing 4.5.6.7-tetrawith a cyclic ortho-diketone.

7. Process of preparing indigoid dyestuifs which comprises condensing 4.5.6.7-tetrachlor-3-hydroxy-l-thionaphthene with an isatin. I 8: Process of preparing indigoid dyestuffs which comprises condensing 4.5.6.7-tetrachlor-3-hydroxy-l-thionaphthene with an isatin-a-chloride.

9. Process of preparing indigoid dyestuffs which comprises condensing 4.5.6.7-tetrachlor-'3-hydroxy-l-thionaphthene with a 5.7- dichlorisatin.

10. Process of preparing indigoid dyestuffs which comprises condensing 4.5.6.7-tetrachlor-S-hydroxy-l-thionaphthene with a 5.7-

dichlorisatin-a-chloride.

with an 11. As new products indigoid dyestuffs having the following atom-grouping wherein C and G represent carbon atoms belonging to the residue ofa cyclic orthodiketone, said products forming brown to violet powders, which are soluble in hot concentrated sulfuric acid and dye cotton tints of excellent properties as to fastness.

12. As new products indigoid dyestuffs having the following atom-grouping:

0:0 7 O m L t wherein C and C represent carbon atoms belonging to the residue of a cyclic orthodiketone, said products forming brown to violet powders,

which are soluble in hot concentrated sulfuric acid and dye cotton tints of excellent properties as to fastness.

13. As new products the indigoid dyestuffs of the general formula:

wherein C and (3 represent carbon atoms belonging to the five membered ring of an isatin residue. i

14. As new products the indigoid dyestuffs of the general formula:

Hlg

wherein the nucleus B may be substituted by halogen.

1.5. As new products the indigoid dyestuffs of the general formula:

16. As anew product the indigoid dyestufi of the formula:

C s N forming a violet powder and dyeing cotton a violet tint of excellent properties as to fastness.

In testimony whereof, We affix our signatures.

ERVVIN HOFFA. HANS HEYNA.

FRITZ MULLER. 

